Electric field modulation of thermovoltage in

single-layer MoS2
Cite as: Appl. Phys. Lett. 105, 253103 (2014); https://doi.org/10.1063/1.4905014
Submitted: 28 October 2014 • Accepted: 04 December 2014 • Published Online: 23 December 2014

Lukas Dobusch, Marco M. Furchi, Andreas Pospischil, et al.

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Appl. Phys. Lett. 105, 253103 (2014); https://doi.org/10.1063/1.4905014 105, 253103

© 2014 Author(s).
 APPLIED PHYSICS LETTERS 105, 253103 (2014)

Electric field modulation of thermovoltage in single-layer MoS2

Lukas Dobusch,1 Marco M. Furchi,1 Andreas Pospischil,1 Thomas Mueller,1
Emmerich Bertagnolli,2 and Alois Lugstein2,a)
1
Institute of Photonics, TU-Wien, Gußhausstraße 27-29, A-1040 Vienna, Austria
2
Institute of Solid State Electronics, TU-Wien, Floragasse 7, A-1040 Vienna, Austria
(Received 28 October 2014; accepted 4 December 2014; published online 23 December 2014)
We study electric field modulation of the thermovoltage in single-layer MoS2. The Seebeck
coefficient generally increases for a diminishing free carrier concentration, and in the case of
single-layer MoS2 reaches considerable large values of about S ¼ 5160 lV/K at a resistivity of
490 X m. Further, we observe time dependent degradation of the conductivity in single layer
MoS2, resulting in variations of the Seebeck coefficient. The degradation is attributable to
adsorbates from ambient air, acting as p-dopants and additional Coulomb potentials, resulting in
carrier scattering increase, and thus decrease of the electron mobility. The corresponding power
factors remain at moderate levels, due to the low conductivity of single layer MoS2. However,
as single-layer MoS2 has a short intrinsic phonon mean free path, resulting in low thermal
conductivity, MoS2 holds great promise as high-performance 2D thermoelectric material. V C 2014

Author(s). All article content, except where otherwise noted, is licensed under a Creative
Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4905014]

The discovery and experimental realization of graphene—
a single layer of graphite—triggered intense research activities
in 2D-material systems.1 A multitude of 2D-materials are
known by now, often showing superior properties compared to
their bulk counterparts. Due to their direct bandgap, single lay-
ered transition metal dichalcogenides, such as WS2, WSe2,
MoSe2, and MoS2, are of high interest for electronic and optoe-
lectronic applications.2 With respect to MoS2, highly sensitive
photodetectors with responsivities up to 880 A/W,3 field effect
transistors (FETs) with an Ion/Ioff ratio of 108,4 flexible tran-
sistors,5 and selective gas-sensors6 have been reported. All
these devices take advantage of the peculiar single-layer-
related properties of MoS2. With regard to thermoelectric prop-
erties, simulations give reason to presume that a maximum
Seebeck coefficient of about 1600 lV/K may be achieved in
layered MoS2.7 Recently, Buscema et al.8 suggested that
photocurrent generation in single-layer MoS2 is dominated by
the photo-thermoelectric effect, indicating remarkably high
Seebeck coefficients of up to 1  105 lV/K, obtained by
laser heating.
In this letter, we report on a giant thermovoltage for
single-layer MoS2, which can be tuned by an external elec-
tric field. By doing so, a thermal bias along single-layer
MoS2 integrated in a back gated FET structure is set up by
Joule heating and measured in situ by two resistive thermom-
eters, allowing precise determination of the Seebeck coeffi-
cient. A maximal Seebeck coefficient of 5160 lV/K is
thus demonstrated, making MoS2 a promising material for
thermoelectric applications.
The effectiveness of thermoelectric materials can be
linked to the dimensionless figure of merit zT, which is pro-
portional to the Seebeck coefficient S, electrical conductivity
r, and absolute temperature T, but inversely proportional to
a)
Author to whom correspondence should be addressed. Electronic mail:
alois.lugstein@tuwien.ac.at
the thermal conductivity j ¼ je þ jl comprising heat trans-
port due to electrons (je) and phonons (jl)
rS2 T
zT ¼ : (1)
j
Competitive thermoelectric materials must have a zT in
the order of 2, corresponding to an energy conversion of
approximately 27% of the Carnot limit. The term rS2 is
referred to as power factor, which, under a given tempera-
ture, quantifies the ability of a material to produce electrical
power. Semiconductors may exhibit a relatively high zT
because of their moderate level of free carrier concentra-
tions.9 Large carrier concentrations lead to high conductiv-
ities, but generally have a detrimental effect on the Seebeck
coefficient, and vice versa for low carrier concentrations.
Modulation of the carrier concentration and thus tuning of
the thermovoltage of semiconductor materials can be
achieved by electrostatic fields, e.g., in FET devices.
In order to investigate the electric field modulated thermo-
voltage of single-layer MoS2, these were integrated into back-
gated FET devices, equipped with resistive heating structures
as shown in the scanning electron micrograph in Figure 1(a).
In addition, this structure enables four-point measurements on
the MoS2 monolayer allowing precise in situ measurements of
the electric field modulated MoS2 resistivity.
For device fabrication, single-layer MoS2 flakes were
deposited by mechanical exfoliation onto highly doped Si
substrates with a 300 nm thick SiO2 layer. Characterisation
of the MoS2 flakes, typically 10 lm2–50 lm2 in size, was
done by optical microscopy10–12 and Raman spectros-
copy.13,14 The electrical contacts and resistive heater struc-
tures were fabricated by electron beam lithography, sputter
metal deposition of Ti/Au (5 nm/130 nm) and lift-off techni-
ques. Prior to the thermo-physical characterization, all
samples were annealed at 200  C for 2 h in He/H2 flow (100
sccm/20 sccm) in order to improve contact reliability.4

0003-6951/2014/105(25)/253103/4 105, 253103-1 C Author(s) 2014

V
253103-2 Dobusch et al.
FIG. 1. (a) SEM image of a typical thermoelectric test device. The single-
layer MoS2 is connected by resistive thermometers (Ti/Au), acting also as
drain and source contacts of the backgated FET device, as well as the four-
point measurement module. A temperature gradient along the MoS2 flake is
achieved by resistive heater elements, inducing a thermovoltage between
source and drain. The thermal bias DT is determined via the resistive Ti/Au
thermometers in a four-point measurement configuration. (b) Electrical per-
formance of a single-layer MoS2 FET with a flake of length l ¼ 6 lm and a
width of w ¼ 5.5 lm. IDS/VDS curves are shown as a function of the
backgate-voltage and the respective transfer response (IDS/VBG) for a full
backgate sweep from VBG ¼ 100 to VBG ¼ 100 V is shown in the inset.
Typical output and transfer characteristics are shown in
Figure 1(b) and the inset, respectively. The back-gated sin-
gle-layer MoS2 FET exhibits n-type behaviour with excellent
field modulation response and a remarkable high ION/IOFF
ratio of 106, in good agreement with previous reports.4,8 The
output characteristic indicates nonlinear behaviour, which
might be attributable to space-charge-limited current15 or
Schottky type16 behaviour of the MoS2-Au contacts. The re-
sistance of these semiconductor-metal contacts, investigated
by four-point measurements, show a strong dependence on
the backgate voltage.14 This field modulated response of the
metallic contacts is attributed to band-bending, its accompa-
nied change in tunnel-efficiency and electrical doping of the
MoS2-Layer, and was taken into account for all succeeding
thermo-physical measurements.
To determine the Seebeck coefficient and to investigate
the field modulation response, the output characteristics of the
backgated MoS2-FET devices were recorded at low VDS with
and without a thermal bias between drain and source.
Differential heating was obtained when the resistive Joule
Appl. Phys. Lett. 105, 253103 (2014)
heater structures were operated at a heating power of approxi-
mately 180 mW leading to thermal biases between 2 K and
6 K, depending on the respective device geometry. The tem-
perature dependency of the resistive thermometers was deter-
mined in separate four-point probe measurements.14 The
temperature coefficient was determined to DR  0.03 X/K
 DT, enabling temperature measurements with an accuracy
of 60.34 K.
Figure 2 shows typical I/V measurements, with a ther-
mal bias of DT ¼ 2.3 K (air, 296 K). Sweeping the backgate
voltage (VBG) in alternating directions, a full I/V sweep was
recorded at each gating value.
Figure 2 and the enlarged view in the upper inset shows
a gate-dependent shift of the I/V curve when a thermal bias
is applied. As expected in the reference measurement, under
isothermal conditions (DT ¼ 0 K), shown in the lower inset
of Figure 2 no such shift of the I/V curve was observed inde-
pendent from the back gate voltage. This shift along the
VDS-axis can be attributed to the thermovoltage VTE of
the MoS2-Au thermocouple. As expected, by reversing the
temperature gradient, a shift in the opposite direction was
obtained.14 The small contribution of the Au-electrodes to
the thermovoltage, which is independent of the gate voltage,
can be subtracted by using
VTE ¼ ðSMoS2  SAu ÞDT; (2)
with SAu ¼ T  6:4 nV=K2 .17,18
To investigate the influence of electric field modulation,
a backgate sweep was performed and the induced conductiv-
ity modulation of the single-layer MoS2 flake was evaluated
using
l
r ¼ ð R  2Rc Þ1 ; (3)
wd
where R and Rc are the device and contact resistance, respec-
tively, d denotes the thickness of single-layer MoS2 of
FIG. 2. I/V characteristics of a backgated MoS2 device with a thermal bias
of DT ¼ 2.3 K as a function of VBG, varied from 40 V to 80 V in steps of
5 V. The intercept at IDS¼0 A allows to extract the thermovoltage VTE. The
enlarged view in the upper inset shows the gate dependency of the thermo-
voltage in more detail (linear fit). The lower inset shows the same device
under isothermal conditions (DT ¼ 0 K) exhibiting no current/voltage shift.
253103-3 Dobusch et al.
0.65 nm,4 and l and w are the channel length and width,
respectively, which were determined by subsequent SEM
imaging. As shown in the upper inset of Figure 2, the ther-
movoltage increases with decreasing backgate voltage VBG.
Figure 3 shows thereof calculated Seebeck coefficients and
their corresponding power factors as a function of resistivity,
modulated by the back gate sweep.
With decreasing backgate voltage, the resistivity of the
n-type single-layer MoS2 device increases (see Figure 1(b))
and thus the Seebeck coefficient. The Seebeck coefficient
generally increases for a diminishing free carrier concentra-
tion,9,19,20 and in case of single-layer MoS2 reaches particu-
larly large values (>500 lV/K) as the sample resistivity
increases above 50 X m. A considerable high Seebeck
coefficient was observed at a resistivity of 490 X m with
S ¼ 5160 lV/K. As shown in the inset of Figure 3, the rise
of the thermovoltage was observed for all investigated sam-
ples, which evidently gives the possibility of tuning the
Seebeck coefficient by field induced resistivity modulation.
Even though the Seebeck coefficients at negative back-
gate voltage, i.e., the high resistive regime, exhibit exceed-
ingly large values, the corresponding power factors remain
moderate. For positive backgate voltage (i.e., in the low
resistivity regime), the power factor shows values of a few
100 nW/K2 m (see Figure 3), whereas the power factors at
negative backgate voltage are about one order of magnitude
lower. However, calculations by Liu et al. show that single-
layer MoS2 has a very short intrinsic phonon mean free path,
resulting in a remarkably low thermal conductivity of
1.35 W/mK.21 Thus, despite the low power factor, MoS2
holds great promise as high-performance 2D thermoelectric
material.
The plot of the field modulated thermovoltage, shown in
the inset of Figure 3, illustrates distinct variations for each
individual single-layer MoS2 device. Further, time dependent
measurements revealed a continuous increase of the Seebeck
coefficient for a given backgate voltage within the first hours
after device processing and the finalizing annealing proce-
dure. We suppose that these variations are the result of
FIG. 3. Semilog plot demonstrating the field modulation of the Seebeck
coefficient (black squares) and the corresponding power factor (red circles)
for a typical single-layer MoS2 device. The Seebeck coefficient varies
between 118 lV/K and 5160 lV/K as a function of the resistivity modu-
lated by sweeping the back gate voltage. The inset shows determined
Seebeck coefficients for 8 investigated single-layer MoS2 thermoelectric
devices.
Appl. Phys. Lett. 105, 253103 (2014)
degradation effects, or defects within the MoS2 layer result-
ing in time dependent variations of the thermoelectric
properties.9 In order to explore these degradation effects, we
measured the transfer characteristic for an as processed
sample as well as for the same sample after several days of
storage in ambient air. Figure 4 shows that the transfer char-
acteristics of the field modulated single-layer MoS2 device
exhibits a significant hysteresis in the VBG dependence as a
consequence of the slow dynamics of surface states and
traps, leading to a time dependent screening of the gate.
However, for the latter measurement one clearly sees a
decrease of the on-current by one order of magnitude, broad-
ening of the hysteresis and a pronounced shift of the thresh-
old voltage towards positive VBG.
The time resolved resistivity measurement, plotted in
the inset of Figure 4, demonstrates a continuous increase of
the resistivity by almost one order of magnitude within the
first 44 h after sample processing and the terminal thermal
annealing. Note that this measurement was performed in a
dark box, and the time dependent resistivity measurements
were started 30 min after closing the darkbox in order to
exclude photoconductivity effects.14,22
In accordance with Zhang et al.,22 we suppose that the
observed degradation effect is due to adsorbates from ambient
air which interact strongly with MoS2, resulting in enhanced
carrier scattering and reduced mobility. By introducing the de-
vice in vacuum and thus removing the adsorbates, the on state
current increases by one order of magnitude, and the threshold
voltage of the FET is shifted towards negative backgate
bias.14 Thus, adsorbates on the surface or at the MoS2/sub-
strate interface appear to act as p-dopants for MoS2 and addi-
tional Coulomb potentials resulting in carrier scattering
increase, thus lowering electron mobility. Recovery of the
device performance can also be achieved by annealing of the
device in H2/He atmosphere at 200  C for 120 min.
FIG. 4. Transfer characteristic of a backgated single-laver MoS2 device
straight after processing and annealing (black solid curve), respectively, and
after storage of the sample for 20 days in ambient atmosphere (red dashed
curve). (VDS ¼ 2 V, sweeping the backgate voltage forward and reverse as
indicated by the arrows.) The time dependent resistivity measurement in the
inset was recorded via a four-point measurement method (VDS ¼ 2 V, VBG
¼ 0 V) straight after annealing and shows a long time degradation
behaviour.
253103-4 Dobusch et al. Appl. Phys. Lett. 105, 253103 (2014)

5
In conclusion, we demonstrate a giant thermovoltage for G.-H. Lee, Y.-J. Ju, X. Cui, N. Petrone, C.-H. Lee, M. S. Choi, D.-Y. Lee,
C. Lee, W. J. Yoo, K. Watanabe et al., ACS Nano 7, 7931 (2013).
single-layer MoS2, which can be tuned by an external electric 6
F.-K. Perkins, A. L. Friedman, E. Cobas, P. M. Campbell, G. G. Jernigan,
field with a maximum Seebeck coefficient of 5160 lV/K, and B. T. Jonker, Nano Lett. 13, 668 (2013).
7
making MoS2 a promising material for thermoelectric appli- C. Lee, J. Hong, M. H. Whangbo, and J. H. Shim, Chem. Mater. 25, 3745
cations. The corresponding power factors remain at moderate (2013).
8
M. Buscema, M. Barkelid, V. Zwiller, H. S. J. van der Zant, G. A. Steele,
levels, due to the low conductivity of single layer MoS2. and A. Castellanos-Gomez, Nano Lett. 13, 358 (2013).
However, the electric conductivity, and hence the power fac- 9
G. J. Snyder and E. S. Toberer, Nat. Mater. 7, 105 (2008).
10
tor, might be significantly increased by a high-k dielectric M. M. Benameur, B. Radisavljevic, J. S. Heron, S. Sahoo, H. Berger, and
passivation as shown in recent works.4,23 Together with the 11
A. Kis, Nanotechnology 22, 125706 (2011).
H. Li, J. Wu, X. Huang, G. Lu, J. Yang, X. Lu, Q. Xiong, and H. Zhang,
low thermal conductivity of single-layer MoS2,21 zT might ACS Nano 7, 10344 (2013).
therefore show superior high values. 12
A. Castellanos-Gomez, N. Agra€ıt, and G. Rubio-Bollinger, Appl. Phys.
The mean variation of the thermovoltage was assigned Lett. 96, 213116 (2010).
13
C. Lee, H. Yan, L. E. Brus, T. F. Heinz, J. Hone, and S. Ryu, ACS Nano 4,
to adsorbates, interacting strongly with MoS2. These adsor-
2695 (2010).
bates act as p-dopants and thus additional Coulomb poten- 14
See supplementary material at http://dx.doi.org/10.1063/1.4905014 for
tials, resulting in carrier scattering increase, thus lowering materials and methods employed, such as Joule heater operation, method
the electron mobility. of thermovoltage measurement, contact resistance, photoconductivity and
degradation effects.
15
S. Ghatak and A. Ghosh, Appl. Phys. Lett. 103, 122103 (2013).
The authors acknowledge financial support by the 16
H. Liu, A. T. Neal, and P. D. Ye, ACS Nano 6, 8563 (2012).
17
Austrian Science Fund (FWF): project No. I 724-N16. The S. Roddaro, D. Ercolani, M. A. Safeen, S. Suomalainen, F. Rossella, F.
authors further thank the Center for Micro- and Nanostructures Giazotta, L. Sorba, and F. Beltram, Nano Lett. 13, 3638 (2013).
18
N. F. Mott and H. Jones, The Theory of the Properties of Metals and
(ZMNS) for providing the clean-room facilities. Alloys (Dover Publication Inc., 1936).
19
W. Liang, A. I. Hochbaum, M. Fardy, O. Rabin, M. Zhang, and P. Yang,
1
K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotkevich, Nano Lett. 9, 1689 (2009).
20
S. V. Morozov, and A. K. Geim, Proc. Natl. Acad. Sci. U.S.A. 102, 10451 P. M. Wu, J. Gooth, X. Zianni, S. F. Svensson, J. G. Gluschke, K. A.
(2005). Dick, C. Thelander, K. Nielsch, and H. Linke, Nano Lett. 13, 4080
2
Q. H. Wang, K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M. S. Strano, (2013).
21
Nat. Nanotechnol. 7, 699 (2012). X. Liu, G. Zhang, Q.-X. Pei, and Y.-W. Zhang, Appl. Phys. Lett. 103,
3
O. Lopez-Sanchez, D. Lembke, M. Kayci, A. Radenovic, and A. Kis, Nat. 133113 (2013).
22
Nanotechnol. 8, 497 (2013). W. Zhang, J.-K. Huang, C.-H. Chen, Y.-H. Chang, Y.-J. Cheng, and L.-J.
4
B. Radisavljevic, A. Radenovic, J. Brivio, V. Giacometti, and A. Kis, Nat. Li, Adv. Mater. 25, 3456 (2013).
23
Nanotechnol. 6, 147 (2011). B. Radisavljevic and A. Kis, Nat. Mater. 12, 815 (2013).